Textile finishing compositions



7 formaldehyde condensation products.

Patented Sept. 22, 1953 2,653,140 .rsx'rms FINISHING COMPOSITION OwenClement Wentworth Allenby, McMasterville, Quebec, Canada, and JamesCarroll Mac- Kenzie, Winchester, Mass., assignors to Canadian IndustriesLimited, Montreal,

Quebec.

Canada, a corporation of Canada No Drawing. Application November 19,1952, Se-

rial No. 321,497. In Canada October 9, 1951 This invention relates tonew textile finishing 'our copending application Serial No. 292,209filed on June 6, 1952, now abandoned.

Durable compositions for the stiffening of cellulosic textile materialshave heretofore been prepared by admixing starch with a thermosettingresin containing groups reactive to the hydroxyl groups of the starchand cellulose molecules. The cellulosic textile materials, whenimpregnated with the starch-resin mixture aid subsequently heated, showthe effects of the stiffening composition for a considerable length oftime due to the water-insolubilization or binding of the starch to thecellulosic material by means of the reactive thermosetting resin.Amongst the thermosetting resins which have heretofore been used, themost effective have been the formaldehyde condensation products such asthe urea-formaldehyde or melamine- However, although these starchfinishes are satisfactory from the point of view of durability, they allsuffer from many disadvantages. For example, when the textile materialsare treatedwith chlorine-containing bleaching agents, the starchfinishes retain chlorine with resultant yellowing of the fabric andconsiderable loss in tensile strength upon ironing due to release ofhydrogen chloride. Furthermore, fabrics treated with these starchfinishes are all harsh to the hand. This is particularly true for starchfinishes con taining polymerized dimethylol urea which are otherwiseconsiderably laundry-fast even in a starch-resin ratio of 100-1.

It has now been found that if in addition to dimethylol urea, there isalso incorporated with starch a water-soluble copolymer of an acid fromthe group consisting of acrylic'acid, methacrylic acid and crotonicacid, an amide selected from the group consisting of acrylamide,methacrylamide and crotonamide, and at least one monoethylenicallyunsaturated compound having the ethylenic group as sole reactive group,the fore going disadvantages are completely overcome. There are thusobtained new textile stiffening compositions which, despite theirretention of chlorine when submitted to the action ofchlorine-containing bleaching agents, do not affect 12 Claims. (01.260-173) the colour or tensile strength of the fabrics upon ironing, andwhich, according to the kind of starch present therein, impart to thefabrics any type of hand desired, e. g. from a full warm hand to a sharpcrisp hand, while possessing the same durability as the above-mentionedstarch finishes of the prior art. It has also been found that these newcompositions act as very effective pigment binders when used in thepigment printing of textile materials.

It is therefore an object of this invention to provide new textilefinishing compositions.

Another object is to provide new durable textile finishing compositions.

A further object is to provide new durable compositions for thestiffening of textile materials.

A still further object is to prov de new durable compositions for thebinding of pigments in the pigment printin of textile materials.

An additional object is to provide new durable compositions capable ofimparting ,to textile materials a wide variety of hands.

Another object is to provide new durable textile finishing compositionswhich, after contact with chlorine-containing bleaching agents anduponironing at high temperatures, do not afiect the colour or tensilestrength of the finished textile materials.

other and additional objects will become apparent hereinafter. i

These objects are accomplished by the new compositions of this inventionwhich broadly comprise starch in admixture with dimethylol urea and awater-soluble thermoplastic copolymer of an acid selected from the groupconsisting of acrylic acid, methacrylic acid and crotonic acid, an amideselected from the group consisting of acrylamide, methacrylamide andcrotonamide, and at least one polymerizable monoethylenicallyunsaturated compound having the ethylenic group as sole reactive group.Preferred compositions suitable for the finishing of both heavy-weightand light-weight fabrics comprise an admixture of starch with dimethylolurea and a water-soluble thermoplastic copolymer of vinyl acetate,crotonic acid and crotonamide and, more particularly, an admixture ofthe latter ingredients in the following weight ratio: starch, 12.7;vinyl acetate-crotonic acidcrotonamide copolymer, 2.3; dimethylol urea,1.

Fabrics impregnated with these compositions and heated at C. in an ovenfor five minutes show excellent ironability, increased body, resistanceto discoloration on ironing after bleaching, and

of starch used, ranges from soft and full to crisp. If printed withpigments into which these compositions have been incorporated ashinders, the fabrics show good colour retention despite numerousintervening launderings.

As previously mentioned, the superior properties of the textilefinishing compositions of this ingention over the compositions of theprior art are due to the incorporation of the water-soluble acid-amidecopolymers into the mixtures of starch and dimethylol urea, andrepresent a totally unexpected result in the art of textile finishesembodying starch and urea-formaldehyde condensates.

The details and manner of practising the invention will be apparent byreference to the following specific examples, it being understood thatthese examples are merely illustrative embodiments of the'invention andthat the scope of the invention is not limited thereto.

Example 1 A water-soluble thermoplastic copolymer containing 86% vinylacetate, 8% crotonic acid and 6% crotonamide was prepared as follows:

215 parts of vinyl acetate were mixed with 20 parts of crotonic acid,2.25 parts of crotonamide and parts of benzoyl peroxide and brought torefiux temperature for 5 minutes. 12.75 parts of crotonamide were thenadded to the refluxing mixture over a 35 minute period after which timethe heating was continued until the temperature reached 105 C. i. e. forapproximately 2 hours. The mixture was maintained at this temperaturefor 30 minutes, a total of 21:9 parts of hutanol being added in thecourse of the reaction to reduce the viscosity of the forming copolymersbefore completion of the copolymerization. The reaction mixture wascooled and mixed with aqueous ammonia so as to form a 20% aqueoussolution of the water-soluble ammonium salt of the vinylacetate-crotonic acid-crotonamide copolymer. This latter copolymer isnot water-soluble in its free-acid form.

.A 5% solution of commercial corn starch was also prepared by stirring16.2 parts of corn starch in 308 parts of water at 95 C. for fiveminutes.

The above starch solution was cooled to 50-60 C. and mixed with parts ofthe above copolymer solution and 4 parts of an 8% solution of dimethylolurea, thus providing a finish containing the starch, copolymer anddimethylol urea in the ratio of 12.7:2.3:0.25.

A x 20".piece of cotton muslin fabric weighing 6 oz. per sq. yard wasthoroughly impregnated at 50-60 C. with the finish and sub- .4 piece ofcotton muslin fabric, weighing 3.8 oz. per sq. yard, was thoroughlyimpregnated with the finish and subsequently air dried and uniformlyironed for 4 minutes at approximately 205 C. with a household iron. Itwas then given an initial wash to remove excess finish and thensubjected to four successive launderings in a standard type rotarywasher. The stiffening finish was thus found to be 65% laundry fast.

Example 3 To a 5% solution of commercial corn starch prepared as inExample 1, there were added 15 parts of the copolymer solution ofExample 1, 4 parts of an 8% solution of dimethylol urea and 0.0032 part(1% by weight of dimethylol urea) of ammonium dihydrogen phosphate. A20" x 20" piece of cotton muslin fabric, weighing 3.8 oz. per sq. yard,was thoroughly impregnated with the finish and subsequently air driedand heated in an oven at 150 C. for 5 minutes. After an initial wash toremove excess finish and four successive launderings, the stiffeningfinish was found to be 67% laundry-fast.

Example 4 I methylol urea ratio of 12.7:23 :0.5, had a laundrysequentlyair dried and uniformly ironed for 2 A 5% solution of commercial cornstarch was prepared as in Example 1 and mixed with 15 parts of thecopolymer solution of Example 1, 4 parts of an 8% solution of dimethylolurea and 0.0016 part (0.5% by weight of dimethylol urea) of ammoniumdihydrogen phosphate, A 20" x 20" fastness of Example 5 A 5% solution ofcommercial corn starch was prepared as in Example 1 and mixed with 15parts of the copolymer solution of Example 1, 16 parts of an 8% solutionof dimethylol urea and 0.0128 part (1% by weight of dimethylol urea) ofammonium dihydrogen phosphate. There was thus obtained a stiffeningfinish having a starchzcopolymerzdimethylol urea ratio of 12362.3:1.

A ,20" x 20" piece of cotton muslin, weighing 2.2 oz. per sq. yard, wasthoroughly impregnated with the finish and subsequently air dried andheated in an oven at 150 C. for 5 minutes. It was then given an initialwash to remove any ex-- cess finish and then subjected to twentysuccessive launderings in a standard-type rotary washer. The finish wasthus found to be 88% laundry-fast after the fourth laundering, 73% afterthe ninth laundering and 50% after the twentieth laundering. The fabricstill showed a full nice hand after the twentieth laundering.

Example 6 Three separate 20" x 20" pieces of cotton muslin, weighing 3.2oz. per sq. yard, were impregnated with the stifi'ening finish ofExample 5, air dried and then heated for 5 minute at 150 0., C., and 98C. respectively. After an initial wash and t wenty repeated launderings,the laundry-fastness of the finish was found to be as follows:

Laundry-fastness Heating Temperature after 5th after 20th launderinglaundering twentieth cycle. starch-urea/formaldehyde resin finishsuffered Example 7 Two separate 20" x 20" pieces of cotton fabric,weighing 4.3 oz. per sq. yard, were impregnated, respectively, with 6.3%by weight of the fabric, of the stiffening finish of Example and 5.6% byweight of the fabric, of a stiffening finish containing starch anddimethylol urea in the ratio The fabrics were then submitted to verydrastic hypochlorite bleaching retaining, respectively 0.046% and 0.060%chlorine. Upon ironing at 400 F. for 5 minutes, substantially nodiscolouration took place in the fabric treated with the finish ofExample 5 whereas the other fabric showed considerable spotty yellowing.The loss in tenacity of the fabric finished with the starch dimethylolurea mixture .was about 44% as against 8% for the other fabric. Thefabric treated with the starch-dimethylol urea mixture was harsh to thehand whereas the other fabric showed a nice full hand.

Example 8 phosphate. The finish thus obtained had astarch:copolymerzdimethylol urea ratio of 12.7 :2.3:1.

Various 8" x 18" pieces of cotton fabric were 7 then impregnated withthe above finish and other similar pieces impregnated with a finishcontaining starch and a urea-formaldehyde resin in the ratio 4:1. Thefabrics were then passed through rubber rolls to remove any excessfinish, air dried and heated in an oven at 150 C. for 5 minutes. Some ofthe fabrics stiffened with the first finish were thensubjected to twentysuccessive launderings in a standard-type rotary washer in order todetermine the laundry-fastness of the finish, while the remainingstiffened fabrics were subjected to twenty laundering and hypochloritebleaching cycles in order to determine the postbleaching effects of bothfinishes upon ironing of the fabrics at approximately 205 C. with ahousehold iron.

The starch-copolymer-dimethylolurea finish was thus found to be 97%laundry-fast after the fifth laundering, 85% laundry-fast after thetenth laundering, 78% laundry-fast after the fifteenth laundering and73% laundry-fast after the twentieth laundering.

As regards post-bleaching effects upon ironing of the fabrics atapproximately 205 C. with a household iron, substantially nodiscolouration took place in the fabrics treated withthestarchcopolymer-dimethylol urea finish even after the twentiethlaundering and bleaching cycle wherethe fabrics treated with thestarchurea/formaldehyde resin finish showed considerable spottyyellowing after the first cycle. The loss in tenacity of the fabricsfinished with the starchecopolymer-dimethylol urea composition was thesame as that of unfinished fabrics subjected to the same number oflaundering and bleaching cycles, i. e.; about 50% after the The fabricstreated with the complete degradation after the twentieth cycle andholes appeared in the fabrics'as early as the third cycle.

Example 9 starch solutions was cooled to 50-60 C. and

mixed with 15 parts of the copolymer solutionof Example 1, 16 parts ofan 8% aqueous solution of dimethylol urea and 0.0128 part (1% by weightof dimethylol urea) of ammonium dihydrogen phosphate. There were thusobtained finishes having a starch:copolymerzdimethylol urea ratio of12.7:2.3:1.

Six 8" x 18" pieces of cotton fabric were impregnated at 50 C. for oneminute with the above finishes, passed through rubber rolls to removeany excess finish, and subsequently air dried and cured in an oven at150 C. for five minutes. The stiffened pieces were then given a wash ina 0.25% castile soap solution containing 0.1% sodium carbonate for 5minutes at 50 C. After three rinses in distilled water, the pieces wereironed dr at approximately 205 C. with a household iron, and redried inan oven at C. for 20 minutes. The following table illustrates the handimparted to the stiffened cotton fabric by each finishas well as theamount of finish impregnated into the fabric, the latter beingdetermined by weighing the pieces before impregnation and after theredrying period.

Example 10 A 5% solution of potato starch was prepared by adding 16.2parts of potato starch to 308 parts of water and boiling the mixture forthirty minutes. The solution was then cooled to 55-60 C. and mixed with11.6 parts of a 25.8% aqueous solution of the copolymer of Example 1, 16parts of an 8% aqueous solution of dimethyl'ol urea and 0.0128 part (1%by weight of dimethylol urea) of ammonium dihydrogen phosphate. To 80parts of the resultant composition, there were then added 20 parts of aphthalocyanine green pigment paste and the mixture was stirred until asmooth paste was obtained. A similar paste was also prepared but using10 parts of phthalocyam'ne pigment instead of 20 parts thereof.

Various 4 yard pieces of cotton, spun viscose rayon, acetate rayon,silk, nylon and polyethylene terephthalate fabric were then printed witheach paste using a Mather and Platt laboratory printing machine, airdried and thereafter'baked in an oven at C. for 5 minutes. Two pieces ofeach fabric, i. e. one piece printed with the 20% paste and one pieceprinted with the 10% paste, were then tested for soaping fastncss bystirring continuously for 15 minutes in water con- 7 minutes at 50 C. inwater containing 0.2% castlle .=oap and 0.1% sodium carbonate followedby Example 11 A water-soluble thermoplastic copolymer con-' taining 86%ethyl acrylate, 8% acrylic acid and 6% methacrylamide was prepared asfollows:

215 parts of ethyl acrylate were mixed with 20 parts of acrylic acid, 15parts of methacrylamide and 5 parts of benzoyl peroxide, and the mixturewas heated at 75 C. for 45 minutes. A small amount of butanol' was'addedat the start to curtail the vigorous reaction and reduce the viscosityof the forming copolymer. The temperature of the mixture was thenallowed to raise slowly to 110 C. over a period of 55 minutes wherebythe copolymerization was completed. The reaction mixture was thereaftercooled and mixed with aqueous ammonia so as to form a 25% aqueoussolution of the water-soluble ammonium salt of the ethylacrylate-acrylic acidmethacrylamide copolymer. This latter copolymer isnot water-soluble in its free-acid form.

A 5% solution of potato starch was also prepared by stirring 16.2 partsof potato starch in 308 parts of water at 95 C. for thirty minutes. Thissolution was then cooled to 5060 C. and mixed with 12 parts of the abovecopolymer solution, 16 parts of an 8% solution of dimethylol urea and0.0128 part (1% by weight of dimethylol urea) of ammonium dihydrogenphosphate. There was thus obtained a stiffening finish having astarch:copolymerzdimethylol urea ratio of l2.'7:2.3:1.

Two 20" x 20" pieces of cotton fabric were then impregnated with theabove finish, air dried and heated in an oven at 150 C. for 5 minutes.After a preliminary wash to remove any excess finish one piece wassubjected to five successive launderings in a standard-type rotarywasher while the other piece was subjected to five consecutivelaundering and hypochlorite bleaching cycles. The durability of thefinish was determined by weighing the fabrics before impregna- ;ion andbefore and after each successive laundering and laundering-bleachingoperation.

The results are shown in the following table in terms of percentage offinish impregnated in the fabrics.

Impregna- It-npregna" tion after Cycle tion after 1aundering launderingbleaching 4. 60 4. 55 4. 35 3. 95 4. 3. 4. l5 2. 85 4. 05 2. 2. s5 2. 0c

Neither fabric showed discoloration upon ironing at 400 F. for 1.5minutes with a household iron.

Example 12 impregnaimpregna- Cycle tion after 322 223;

W-" bleaching Percent Percent Each fabric had a full, pleasant handimparted thereto by the finish, and showed no discoloration upon ironingat 400 F. for 1.5 minutes with a household iron.

As illustrated by the foregoing examples, the durable finishes of thisinvention are readily and simply prepared as well as applied to textilematerials and despite their retention of chlorine upon contact withhypochlorite bleaching agents, they do not produce any discolouration ofthe textile materials upon ironing thereof or any appreciable loss oftensile strength. Example 6 shows that it is preferable, from the pointof view of durability, to bake the finishes at a temperature of at leastC. The baking temperature can of course be raised over 150 C. withresultant shortening of the baking time. The presence of an acid bakingcatalyst does not appear to be essential for promoting the durability ofthe finishes as shown by Examples 1, 2 and 3.

Examples '7, 8 and 9 show the unexpected beneficial effects obtained bythe incorporation of the water-soluble acid/amide copolymers into theknown finishes containing starch and ureaformaldehyde condensationproducts. As regards the finishes of this invention when used for thepigment printing of textile materials, they are not deemed superior toprior pigment binding agents because of their bleach-stability sincepigmented textile materials are not generally subjected to the action ofbleaching agents. Their superiority over the pigment binders of theprior art is rather based on their initial water-solubility and henceease of application, their heat convertibility to which they owe theirdurability, and also the wide variety of hands imparted thereby to thepigmented fabrics.

Although the examples show finishes containing acid/amide copolymers ofonly one composition, the composition of these copolymers may be variedwithout afiecting the durability and other beneficial properties of thefinishes. The copolymers should, however, be soluble in water, viz. intheir ammonium salt form, so as to be readily admixed with the aqueoussolutions of starch and dimethylol urea. It is also possible to vary thecomposition of the finishes by changing the ratio of the variousingredients thereof. As above indicated, however, finishes having astarch: copolymer dimethylol urea ratio of 12.7:2.3:1, and moreparticularly a starchzvinyl acetate/crotonic acid/ crotonamidecopolymendimethylol urea ratio of 12.7:2.3:1, have been found to be verysuitable for both heavy-weight and light-weight textile materials.

Amongst the polymerizable monoethylenically unsaturated compounds havingthe ethylenic group as sole reactive group which can be used ascomponents of the water-soluble copolymers of the finishes, there may bementioned methyl acrylate. ethyl acrylate, propyl acrylate, butylacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,butyl methacrylate, vinyl acetate, vinyl propionate, styrene, vinylnaphthalene, etc.

As many apparently widely different embodiments of this invention may bemade without departing from the spirit and scope thereof, it

' is to be understood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

Having thus described our invention what we claim is:

1. A textile finishing composition comprising as essential ingredientsstarch, dimethylol urea, and a water-soluble 'salt of a thermoplasticcopolymer of an acid selected from the group .con sisting of acrylicacid, methacrylic acid and crotonic acid, an amide selected from thegroup consisting of acrylamide, methacrylamide and crotonamide, and atleast one other polymerizable monoethylenically unsaturated compoundselected from the group consisting of styrene, vinyl acetate and loweralkyl esters of acrylic acid and methacrylic acid.

2. A textile finishing composition comprising as essential ingredientsstarch, dimethylol urea, and a water-soluble salt of a thermoplasticcopolymer of crotonic acid, crotonamide and vinyl acetate.

3. A textile finishing composition comprising as essential ingredientsstarch, dimethylol urea,

and a water-soluble salt of a thermoplastic copolymer of crotonic acid,crotonamide and vinyl acetate, in the following weight ratio: starch12.7; dimethylol urea, 0.25-1.0; copolymer salt, 2.3.

4. A textile finishing composition comprising as essential ingredientsstarch, dimethylol urea, and a water-soluble salt of a thermoplasticcopolymer of crotonic acid, crotonamide and vinyl acetate, in thefollowing weight ratio: starch, 12.7; dimethylol urea, 1.0; copolymersalt, 2.3.

5. A textile finishing composition comprising as essential ingredientsstarch, dimethylol urea,

weight ratio: starch, 12.7; dimethylol urea, 1.0;

copolymer salt. 2.3.

7. A textile finishing composition consisting essentially of an aqueoussolution of starch, dimethylol urea, and a water-soluble salt of athermoplastic copolymer of an acid selected from. the group consistingof acrylic acid, methacrylic acid and crotonic acid, and amide selectedfrom the group consisting of acrylamide,'methacrylamide and crotonamide,and at least one other polymerizable monoethylenically unsaturatedcompound selected from the group consisting of styrene, vinyl acetateand lower alkyl esters of acrylic acid and methacrylic acid.

8. A textile finishing composition consisting essentially of an aqueoussolution of starch, d1- methylol urea, and a water-soluble salt of athermoplastic copolymer of crotonic acid, crotonamide and vinyl acetate.

9. A textile finishing composition consisting essentially of an aqueoussolution of starch, di-

11.'A textile finishing composition consisting essentially of an aqueoussolution of starch, dimethylol urea, and a water-soluble salt of atriermoplastic copolymer containing 8 crotonic acid, 6% crotonamide and86% vinyl acetate, in the following weight ratio: starch, 12.7;dimethylol urea, 1.0 copolymer salt, 2.3.

12. A textile finishing composition consisting essentially of an aqueoussolution of starch, dimethylol urea, and the ammonium salt of athermoplastic copolymer containing 8% crotonic acid,

6% crotonamide and 86% vinyl acetate, in the followingweight ratio:starch, 12.7; dimethylol urea, 1.0; copolymer salt, 2.3.

OWEN CLEMENT WENTWORTH ALLENBY. 'JAMES CARROLL MACKENZIE- ReferencesCited in the tile of this patent Um'mn STATES PATENTS Name Date Acre eta1. June 12, 1945 Number

1. A TEXTILE FINISHING COMPOSITION COMPRISING AS ESSENTIAL INGREDIENTSSTARCH, DIMETHYLOL UREA, AND A WATER-SOLUBLE SALT OF A THERMOPLASTICCOPOLYMER OF AN ACID SELECTED FROM THE GROUP CONSISTING OF ACRYLIC ACID,METHACRYLIC ACID AND CROTONIC ACID, AN AMIDE SELECTED FROM THE GROUPCONSISTING OF ACRYLAMIDE, METHACRYLAMIDE AND CROTONAMIDE, AND AT LEASTONE OTHER POLYMERIZABLE MONOETHYLENICALLY UNSATURATED COMPOUND SELECTEDFROM THE GROUP CONSISTING OF STYRENE, VINYL ACETATE AND LOWER ALKYLESTERS OF ACRYLIC ACID AND METHACRYLIC ACID.